Composite structure

ABSTRACT

A composite structure having a number of thermoset resin containing elements and a number of thermoplastic elements and at least one interface between the thermoset resin containing elements and the thermoplastic elements is provided. The thermoset resin containing elements and the thermoplastic elements have functional groups at the interface which bond to each other when the composite structure is cured and the functional groups are independently selected from amines, carboxylic acids, acid anhydrides, oxiranes, and derivatives thereof in their non-bonded condition. Additionally, a blade having such a composite structure is provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of European Application No.EP13161600 filed Mar. 28, 2013, incorporated by reference herein in itsentirety.

FIELD OF INVENTION

The invention describes a composite structure based on a number ofthermoset resin elements, in particular a composite structure for theuse in a blade, for example as a part of a wind turbine system, and to ablade comprising such a composite structure.

BACKGROUND OF INVENTION

Blades for wind turbine systems were traditionally made of severalfiber-reinforced resin containing components. Commonly, blades arecasted in one piece or in several pieces, for example two shells, whichare then glued to each other. The dominant processing method ofproducing the resin containing components such as the blades is vacuumresin infusion. An alternative processing method is prepreg molding withwoven or unidirectional glass fabrics which already contain the resin asthe matrix material.

In order to withstand large and repeated loads, the wind turbine bladeswere conventionally made from thermoset resins having good mechanicalproperties. Therefore, typical resin containing components werelaminates composed of several reinforced resin layers overlaying eachother and building up the finished blade structure. Generally, the bladematerials were selected to provide a high rigidity and resistance totorsion and fatigue to the blades. Because of the mechanical performanceof such blades, epoxy resins were typically used, especially, if longerblades of more than 40 or 50 m were manufactured. Similar techniques andresin materials for composite structures were applied in the automotiveindustry for example.

The amount of reinforced resin material used in such thermoset elementsmake the resultant parts heavier than corresponding non-reinforcedparts, wherein the amount of reinforcement used generally depends on themechanical requirements. In the patent application US 2002/01787702 A1,composite parts for automotive applications have been proposed which aremade of a combination of a thermoplastic first layer and a secondthermoset layer. The first layer made of a thermoplastic materialprovides a good surface finish and reduces overall part weight, whilethe second layer made of a thermoset resin provides a good strength andrigidity to the composite part. The thermoplastic layer and thethermoset layer are bonded to each other by the use of an adhesion siteactivated by a component of the unreacted thermoset resin that acts on acomponent of the thermoplastic resin or by a mechanical penetration of athin, porous layer by the two resins. Styrene groups are used as suchactive sites.

The incorporation of some thermoplastic elements into a compositestructure as has been described in the field of automotive applicationswas also considered in the field of wind turbine blades. Theseconsiderations were made either for enhancing processing capabilities orfor achieving an effect of the element in the use of a laminate.

In wind turbine blade applications, however, it was investigated thatthe resulting mechanical properties of the laminate material comprisingthermoplastic and thermoset resins were affected to some extent, mostoften negatively. This was caused mainly from inferior materialproperties of the thermoplastic or inferior interface properties betweenthe thermoplastic and the thermoset resin layers. Therefore, if suchcomposites were applied, the amount of thermoplastic materials in thecomposite structures was reduced as much as possible.

SUMMARY OF INVENTION

It is therefore an object of herein to overcome the afore-mentioneddisadvantages of common composite structures comprising both a thermosetresin element and a thermoplastic element and, especially, to improvethe mechanical properties of such a composite material.

According to aspects of the invention, the composite structure comprisesa number of thermoset resin containing elements and a number ofthermoplastic elements and at least one interface between the thermosetresin containing elements and the thermoplastic elements. A number meansin the context of the present invention that one or more, for example,at least two, more than two or multiple elements of the same type, thatmeans thermoplastic or thermoset resin containing elements, arecomprised in the structure. They can be arranged next to each other orin consecutive order of different types like a stacked laminate ofthermoplastic elements and thermoset resin containing elements.Therefore, one or more interfaces between the thermoset resin containingelements and thermoplastic elements, respectively, are comprised in acomposite structure according to the invention.

As the connection of the thermoset resin containing elements and thethermoplastic elements at the interfaces are crucial for the materialproperties of the composite structure, the thermoset resin containingelements and the thermoplastic elements comprise functional groups atthe interface which bond to each other when the composite structure iscured or hardened. The mechanical properties, e. g. the rigidity of thecomposite material, are improved by the reactive groups introduced intothe thermoplastic material, in particular a resin material, or thethermoset resin or both materials or resins which can form stable bondsbetween each other.

The functional groups are specifically selected from chemical groupswhich are harmless to the workers at the manufacturing sites and do notincrease work related risks when correctly handling the different resinmaterials. More particularly, with the term “harmless” it is meant thatthe functional groups are in general considered to be most likelyharmless, for example if they are handled in a “diluted” form in athermoplastic element or for producing such an element under controlledconditions. Exemplified functional groups which can be introduced intothe resin elements are independently selected from amines, carboxylicacids, acid anhydrides, oxiranes, and derivatives thereof in theirnon-bonded condition. Accordingly, the above-mentioned functional groupsreact with the respective counter groups in the elements to be connectedso that they are no longer present in their non-bonded or curedcondition in the finished products. In the finished products, therespectively generated reacted groups essentially are present while theunreacted groups may be present in a non-significant amount only asside-products.

An advantage of incorporating the above-exemplified functional groupsinto the thermoplastic element and/or the thermoset resin containingelement is that they are most likely harmless or non-toxic for theworkers or can be handled without extensive safety measures. Any ofthese groups can bind to the resin component or an auxiliary componentin the respective resin element or they can be selected such that two ofthese functional groups bind to each other, thereby connecting thethermoset resin containing element with the thermoplastic element.

In another aspect of the present invention, a blade comprising acomposite structure according to the invention as has been describedbefore is provided. Such a blade is advantageous over current bladetechnology because it is now possible to include thermoplastic elementsinto the thermoset resin structure or providing thermoplastic parts atthe surface of the blade. In both alternatives, the thermoplasticelement is connected to the thermoset resin containing element(s) bymeans of covalent bonds generated from the respective functional groupsduring the curing of the resins in at least the thermoset resincontaining elements. The thermoplastic elements can be provided inside alaminate structure in the form of sheets or foils, for example. Thus,the mechanical properties of a blade composed mainly of thermoset resincontaining elements can be adjusted in a wide manner by introducing asignificant amount of thermoplastic elements, while adding otherproperties to the structure that would be very difficult or impossibleto introduce into the finished product using the thermoset resincomponent only. If the thermoplastic element is provided at the surfaceof a blade, special elements for improving the aerodynamic of a blade orproviding additional functionality to a blade can be mounted during themanufacturing process of a blade. Generally, a high strength of theconnection at the interface between the thermoset resin containingelement and the thermoplastic element can be provided by the use of thespecific functional groups according to the general concept of theinvention.

Particularly advantageous embodiments and features of the invention arerevealed in the following description. Features may be combined asappropriate to give further embodiments not explicitly described herein,but easily derivable from the context of the described preferredembodiments.

In a preferred embodiment, the composite structure comprises a thermosetresin containing element comprising a two or three component systemhaving at least one resin containing component and at least onehardener, for example one resin component together with two hardeners,wherein the hardeners are not stable in a mixture of them. When a two orthree component system is used, the functional groups of thethermoplastic element bind either to the resin component or to thehardener component(s). Alternatively, the functional groups can beadapted such that they can bind to the two components, the resincomponent and the hardener, in order to improve the connection betweenthe thermoset resin containing element and the thermoplastic element.The connection is stronger if a higher number of bonds per surface areaor two or more different types of bonds have been generated at theinterfaces in the finished product. From the perspective of savingcosts, it is easier and sufficient, if the functional groups aregenerally provided at one of the elements, e. g., the thermoplasticelement, and have the function of bonding either to the resin componentor the hardener of the respective other resin element, in this case thethermoset resin containing element, for example. This allows that onlyone resin element may be particularly provided with specific functionalgroups while the other element has respective counterparts of thefunctional groups in their general structure or in a part of theirgeneral structure.

The resin containing component used in a composite structure asdescribed before preferably comprises an epoxy resin as the thermosetresin material. The advantage of epoxy resins is that the epoxide groupspresent in the monomers, oligomers or polymeric partial structures, suchas side changes thereof, comprise epoxide groups or remaining epoxidegroups which are reactive against amines, carboxylic acids, and acidanhydrides. If an epoxy resin is used in the thermoset resin element, atwo component system having an epoxy part and a hardener part ispreferred. The hardener is advantageously based on an amine or comprisesdifferent amines. It is preferred to use an amount of hardener which issufficient for curing the epoxy resin and optionally providingadditional functionality to the thermoset resin element. In addition,the resin materials used and the hardeners used are generally reactiveat temperatures above room temperature so that the thermoset resinelements can easily be handled by room temperature and can be cured atelevated temperatures, e. g. at above 50° C. or higher preferably befrom 50 to 120° C. The resins and hardeners used are commerciallyavailable from several suppliers and are well known to the skilledperson.

Therefore, it is preferred that the composite structure includes athermoplastic element comprising functional groups reactive with theresin component or with the hardener. In case of epoxy resins as thethermoset resin component in the thermoset resin containing element, thethermoplastic element is advantageously provided with functional groupsincluding, but not limited to, amines, carboxylic acids, and acidanhydrides. In epoxy resin mixtures, the hardener is preferably based onamines. Thus, preferred examples of functional groups that react withepoxy hardeners include, but are not limited to, oxiranes, carboxylicacids, and derivatives thereof.

The functional groups or materials as exemplified before provide achemical bond between the thermoplastic element and the thermoset resincontaining element to ensure improved interface strength. The chemicalbonds are covalent bonds which provide an optimum strength to theconnection between the two elements. The bonds avoid totally or lower,at least to a significant part, the risk of delamination of therespective elements at their interface as it has been observed in thecurrent technology.

The thermoset resin containing element and the thermoplastic element maybe provided with reactive parts, preferably at their surfaces, such thatthe reactive parts comprise the functional groups as specified before.If the functional groups are provided at the surface of the elementsthey can easily be presented to the reactive counterparts at the elementto be connected therewith. The reactive parts with the functional groupsmay be inherently provided in the resin elements, e. g. in side chainsof the resin monomers, oligomers or polymers or in the hardener.Alternatively, they may be introduced in the resin element structure orat the surface thereof, by different techniques, for example by formingof co-polymers, interpenetrating networks, compounding or surfacemodification.

The composite structure according to another preferred embodimentcomprises a laminate of two or more thermoset resin containing elementsand one or more thermoplastic elements. Laminate means in the context ofthe present invention that a thermoset resin containing element layerand a thermoplastic element layer are arranged next to each other,followed by at least one additional thermoset resin containing elementlayer arranged next to the thermoplastic element layer. Thus, a laminatecomprises at least two interfaces between a thermoset resin containingelement and a thermoplastic element. Of course, more than three resinlayers may be provided in a laminate so that a consecutive stack ofthermoset resin containing element layers and thermoplastic elementlayers is provided. At each interface of such a laminate, the functionalgroups in the resin elements generate a chemical bond between the tworesin elements to improve the strength at the interface and to avoiddelaminating effects during use.

It is advantageous that the thermoset resin elements are reinforcedresin elements having a reinforcing structure such as a fabric and aresin component which may be present in the element before curing(prepreg process) or may be impregnated during the curing process(injection molding process). In view of the invention, fabric is a layerof fibres that will strengthen the resin element. The layer is composedof stitched or woven fibres or comprises individual fibres placedtogether. Exemplified fibres preferably used in the field of compositestructures, especially for blades for wind power technology, are glassfibres such as e-glass or high modulus glass fibres.

In an alternative embodiment of the composite structure according toaspects of the invention, the thermoplastic element is arranged at thesurface of a thermoset resin element. This embodiment allows theaddition of constructional means mainly made of thermoplastic materialsat the surface area of thermoset resin elements. By the use of thefunctional groups in the uncured composite structures, theconstructional means can be connected to the thermoset resins by meansof chemical bonds resulting in improved interface strength. Thus, newlaminate properties based on a combination of thermoplastic elements andthermoset resin containing elements can be achieved while the safety ofthe workers at the manufacturing sites can be improved or guaranteed atthe same time.

These advantageous mechanical properties and the ease of manufacturingpossibilities predispose the composite structures according to theinvention for being used as blades, especially for blades being part ofa wind turbine system. The high strength and reliability of theinterfaces enables the production of blades having a better performance,for example a better aerodynamic profile.

Furthermore, it is preferred that blades with additional elements at thesurface of the blades can be manufactured even if the additionalelements comprise at least partly a thermoplastic material or are mainlymade of a thermoplastic material, for example in order to provide asufficient flexibility to this additional element. In this case, it ispreferred that the blade according to the invention comprises athermoplastic element as this additional element, wherein thethermoplastic element is part of an aerodynamic improving element. Suchelements are known in current blade technology, for example asDinoShells (trademark of Siemens), DinoTails (Trademark of Siemens) orvortex generators. DinoTails, DinoShells, and vortex generators areadd-ons that make the blades more efficient because they maximize theaerodynamic performance and robustness with regard to roughnesssensitivity.

DinoTails are separated flaps, shaped like a tail fin on a stegosaurus,which are generally placed close to the blade tip to make the bladesquieter and enhance lifting performance.

DinoShells are a combination of a flap known from racecars and ordinaryflaps. They usually have an overlaid seashell structure. Therefore, theyare fixed control surfaces attached near the trailing edge of the bladesurfaces in order to increase lifting capacity especially on the thickpart of the blade closest to the hub.

Vortex generators are aerodynamic turbulators designed to improve theflow of air over the wind turbine blades. They generally enhance theaerodynamic performance of a blade and are usually used on the part of ablade closest to the hub.

Of course, the use of the composite structures as described before inblades is not limited to the afore-mentioned specific embodiments, butcan be used to add additional aerodynamic elements into or on thesurface of blades.

Other objects and features of the present invention will become apparentfrom the following detailed descriptions considered in conjunction withthe accompanying drawings. It is to be understood, however, that thedrawings are designed solely for the purposes of illustration and not asa definition of the limits of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic view of the cross-section through the compositestructure according to FIG. 1 in a state before assembling the thermosetresin elements and the thermoplastic element;

FIG. 2 shows a schematic view of the cross-section through a compositestructure according to the invention in a state after assembling andcuring;

FIG. 3 shows a schematic view of the cross-section through a compositestructure and the chemical reactions occurring at the interfaces thereofduring the curing process.

DETAILED DESCRIPTION OF INVENTION

In the diagrams, like numbers refer to like objects throughout. Objectsin the diagrams are not necessarily drawn to scale.

FIG. 1 shows a schematic view of the cross-section through a compositestructure according to the invention in a state before assembling thethermoset resin containing elements 1 and the thermoplastic element 2.The composite structure comprises two thermoset resin containingelements 1 each composed of a number of fabric layers placed on eachother in a parallel configuration to build up the two thermoset resinelements. The fabric layers may be formed by fabrics with or without athermoset resin content. If the fabrics still contain a thermoset resincontent, they are usually called prepregs. Otherwise, the fabric layersmay be arranged together with the thermoplastic elements and thenimpregnated with thermoset resin. This is called resin injectionprocess. Of course, both processes can be combined.

Between two thermoset resin containing elements 1, a thermoplasticelement 2 can be arranged before curing will take place. This situationis shown in FIG. 1.

FIG. 2 shows a schematic view of the cross-section through a compositestructure according to FIG. 1 in a state after assembling and curingeither by means of the prepreg process or the resin injection process.The composite structure obtained comprises a thermoplastic element 2between two thermoset resin containing elements 1 which are nowconnected by a strong bond at the interfaces 3 between the thermosetresins containing elements 1 and the thermoplastic elements 2. The bondsgenerated due to the curing reaction are covalent bonds between thefunctional groups which were present at the interface 3 between thethermoset resin containing elements 1 and the thermoplastic elements 2before curing. Therefore, the two thermoset resin containing elements 1are strongly fixed by means of the thermoplastic element 2 therebetween.

FIG. 3 shows a schematic view of the cross-section through a compositestructure and the chemical reactions occurring at the interfaces 3between the thermoset resin containing elements 1 and the thermoplasticelement 2 during the curing process. In FIG. 3, it has exemplarily showna reaction of a thermoplastic element 2 having amine groups at sidechains thereof with epoxide groups of the thermoset resin containingelements 1, for example elements composed of epoxy resins with remainingside chains with epoxide functionality.

The skilled person knows from the afore-mentioned description thatvarious changes as to the functional groups are possible. For example,the groups can be changed and amine functionality can easily be providedat the thermoset resin element surface, for example by using an aminehardener.

Although the present invention has been disclosed in the form ofpreferred embodiments and variations thereon, it will be understood thatnumerous additional modifications and variations could be made theretowithout departing from the scope of the invention. For the sake ofclarity, it is to be understood that the use of “a” or “an” throughoutthis application does not exclude a plurality, and “comprising” does notexclude other steps or elements.

The invention claimed is:
 1. A composite structure comprising a numberof thermoset resin containing elements and a number of thermoplasticelements and at least one interface between the thermoset resincontaining elements and the thermoplastic elements, wherein thethermoset resin containing elements and the thermoplastic elementscomprise functional groups at the interface which bond to each otherwhen the composite structure is cured and the functional groups areindependently selected from amines, carboxylic acids, acid anhydrides,oxiranes, and derivatives thereof in their non-bonded condition; whereinthe thermoset resin containing element comprises a two or threecomponent system having at least one resin component and at least onehardener; and wherein the thermoplastic element comprises functionalgroups reactive with the resin component or with the hardener.
 2. Thecomposite structure according to claim 1, wherein the resin componentcomprises an epoxy resin.
 3. The composite structure according to claim1, wherein the composite structure comprises a laminate of two or morethermoset resin containing elements and one or more thermoplasticelements.
 4. The composite structure according to claim 1, wherein thethermoplastic element is arranged at the surface of a thermoset resincontaining element.
 5. The composite structure according to claim 1,wherein the functional groups at the interface bond to each other bycovalent bonds generated when the composite structure is cured.
 6. Thecomposite structure according to claim 3, wherein the one or morethermoplastic elements comprise one or more sheets.
 7. A bladecomprising a composite structure, said composite structure comprising: anumber of thermoset resin containing elements and a number ofthermoplastic elements and at least one interface between the thermosetresin containing elements and the thermoplastic elements, wherein thethermoset resin containing elements and the thermoplastic elementscomprise functional groups at the interface which bond to each otherwhen the composite structure is cured and the functional groups areindependently selected from amines, carboxylic acids, acid anhydrides,oxiranes, and derivatives thereof in their non-bonded condition; whereinthe thermoplastic element is part of an aerodynamic improving element.8. The blade according to claim 7, wherein the blade is part of a windturbine system.
 9. The blade according to claim 7, wherein thethermoplastic element forms a surface of the blade.
 10. A compositestructure comprising a number of thermoset resin containing elements anda number of thermoplastic elements and at least one interface betweenthe thermoset resin containing elements and the thermoplastic elements,wherein the thermoset resin containing elements and the thermoplasticelements comprise functional groups at the interface which bond to eachother when the composite structure is cured and the functional groupsare independently selected from amines, carboxylic acids, acidanhydrides, oxiranes, and derivatives thereof in their non-bondedcondition; wherein the thermoset resin containing element comprises atwo or three component system having at least one resin component and atleast one hardener; wherein the thermoplastic element comprisesfunctional groups reactive with the resin component and with thehardener.
 11. A composite structure comprising a number of thermosetresin containing elements and a number of thermoplastic elements and atleast one interface between the thermoset resin containing elements andthe thermoplastic elements, wherein the thermoset resin containingelements and the thermoplastic elements both comprise functional groupsat the interface which bond to each other when the composite structureis cured and the functional groups are independently selected fromamines, carboxylic acids, acid anhydrides, oxiranes, and derivativesthereof in their non-bonded condition; wherein the thermoset resincontaining element comprises a two or three component system having anepoxy resin component and at least one hardener; wherein the functionalgroups of the thermoplastic elements that bond to the at least onehardener are selected from oxiranes, carboxylic acids and derivativesthereof.
 12. A composite structure comprising a number of thermosetresin containing elements and a number of thermoplastic elements and atleast one interface between the thermoset resin containing elements andthe thermoplastic elements, wherein the thermoset resin containingelements and the thermoplastic elements both comprise functional groupsat the interface which bond to each other when the composite structureis cured and the functional groups are independently selected fromamines, carboxylic acids, acid anhydrides, oxiranes, and derivativesthereof in their non-bonded condition; wherein the functional groups ofthe thermoplastic elements at the interface comprise amines.
 13. Thecomposite structure according to claim 12, wherein the functional groupsof the thermoset resin containing elements at the interface compriseepoxides.
 14. The composite structure according to claim 13 whereincovalent bonds are generated between the amines and the epoxides at theinterface when the composite is cured.